Fungicidal composition



United States Patent Q 2,772,260 atented No ZZ, 195.6

=,- JZi-LRIAJ Udawi lll on a quantum maze FUNGICIDAL COMPOSITION Charles C. Yeager, Glen Ellyn, Ill., assignor to Scientific Qi Compound n Compa y, lust-t a, corporation of v ..,.1;,, 1 hr J No. Drawing. Application October 22, 19.53,

s liial NQ- 339,14

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ir ine'salt of a rosin amine and water insoluble carb ox ylic acids oa p produced by reacting a water insoluble metal soap of a carboxylic acid with a complex nietal ammine salt of a rosin amine formed by reacting a rosin amine with a metal salt capable of forming complexes with ammonia, have a fungicidal activity on plants, textiles, paper, athe w od, e c, ha s, in general, hi h than that f the component materials from which the reaction products ptepa cd- Additionally, the. novel reaction products ofthe present invention are not phytotoxic Qt exhibit substantially no phytotoxicity and hence are particularly suitable for incorporation in compositions designed for use as fungicidal plant sprays, or in other fungicidal and insecticidal compositions designed for the treatment of plant life. The novel reaction products of the present invention may be incorporated in varnishes, sealers, lacquers, paints, and the like, or in resins, waxes, greases and'the like, and the resulting products arethereby'made fungus-resistant In general, the novel reaction products of the present invention are prepared by reacting a complex metalammine salt of a rosin amine with a Water iiisol lible's'oap' of acarboxylii: acid, in the presence" or absence'of a solvent, at-an elevated temperature at least suflicient to place the reactants into' homogeneous solution; It preferr'dt'o carry out the reaction at a temperature in the bidet of about 250 to 400 F. Lower temperatures may be used, but at'a sacrifice of time. Higher" 'te'ir'ipera'tufesfup to the lowestd'ecompo'sit'ion temperature or the reactants, maybe used, if' des ired. 4 A

The proportions of the reactants may be varied widely, as desired. Thus, stoi'cliiometrical 'propofti "n s o'r an e'xcess of one reactant with're'spectt'o theotlie'i' may be used.

' 'The' complex metal ammine salt -of a ios i i'amin'e gray be introduced as such intothe reaction with' thewatei" insoluble soap or it maybe formed'in'situ in thereac'tion mix. These complex metal ammine salts by feagsting' rosin with a watensoluble metal salt capable o'f'lfo r'ming complexes with ammonia, asthfe 'c pp'er, iin'c, 'ehrem'iuh, mercury, s'ilye'rjaliiinimir'ri'firon, cobalt; nickel, etc., salts, asdes cribed in Pat eii'tNoj'. 2,513,:429, granted July 4, 1950;" "Examples of the e soluble 'salts are copper acetate, zinc acetatg the ace ates of the other named metals, and foi mate, chloracetatefbronioac'e chloride, "sulfate, borate carbonate, thiocyanate," eta, salts capable or forming complexes'wi-th' r a." Heart of s' s n amini s'ivh h n ey us t a qmp x m a were a teams are fi cs 't i it at on n ud h e n when rom isibs' 'lqr awn res erfl a i us a fig ade sii h s deh crq sna s W 99 hydrogenated rosin, or'polym'erized "rosin."

2 am 2:! 2 2. 2: th wine de ed om the u e rosin a i in. whi h abi y m i t e m ne d r v d. time abi acid, ehitdwab et miss is he am ne er ved r m q h sl eabi e a l yd pab e r am ne is t e ami e de d dihy wab ct a n an d abietyl amine is the amine derived from tetrahydroabietic acid. And they may be the secondary tertiary rosin amines in which the hydrogens attached to the nitrogen are replaced by lower alkyl and alkylol groups, such as me hyl le ro.ahit'at'yl mine, ethy c ydroa i tyl mliie, d me hy'l 'de t ab y am ne sli r ehyd oabie tyl amine, isopropyl dehydroabietyl amine, butyl dehydroabietyl amine, hydroxymethyl dehydroabietyl amine, hydroxyethyl dehydroabietyl amine, and di(l ydroxyethyl) dehydroab'ietylarnine: Similar secondary andter'tiary rosiri'arriines having the nucleus of athletic acid, dihydroabietic acid, tetrahydroabietic acid, and polymerized abietic' acid may also be used, as may also the other amines referred to in the aforesaid patent.

'Thdcfo pplex' metal ammine salts which may be used as areactant to form the reaction products of the present invention may be any one of those specifically named in the. aiorfesaidgatenh'for example, dehydro'abiet yl ammino ug c a'g'e a e, dehydroapietyl 'arnrnino Zinc chloride, ti hydroaliieftyh'ammino zine acetate dehydroabietyl ainchloridie, dehy' roabieiyl ammino mercuric acetate eta; ansth ss ean as i h m b st ait i 'n o po n The ateti i2 l i'sqap's oi carhQ i i whicH are new ri q 'a t ina l 'ttl ag w th he we n; n Lit-I tion are t! ter n bl ef soaps qt a'n et'al (immature; p-fqrt'iiiii'g acid or'fa mixture of such #95 may scape of a c um; 11 1 it itmfime g th lead aditt fltti; S ica th i a'ese se alt, nose in an tin, a ifii i a d l te- The 1%, fe'rred' -arts at? the cqfi fz i and nickel soaps'becau'se'th'e results Qbtiiiiicd lyith these .93% are. sens -9t to th se chaise 1e withthe Q helr scab Ieferm IQhQ s a i u ed it! f r ing h ss-ai water-insoluble metalsoap s include inono-carboxylic acids h as a east Ma iq?! ti th a b' xyl d arid ieipg 'Qth wis'e subs ituted tha with a hy arbon retrial arid. th hy roxyl radic l, su h apr acid, icapr'ylic acid, capric acid, laur'ic acid, inyristic 'acid, palmistic acid,'s tearic acid, oleic acid, linoleic' acid, liliolenic acid, palmitoleic acid, mel issic acid, hydroxystedric cid, rici ql c ac d, an like; and mixtures thereof The e er d seanr tih n ti al o ma ri a;

, thes satu ate?! 5 5. unsa u ed high a iph ti a ids containing from twelve to'eig hteen carbon atoms, and rosin. Other soap-forming fatty acids which may be used in forming the metal soaps used in accordancewith the present invention are the mixed higher fatty acids defiYa from a im l Qt ve eta le seems s h a fo e emP di e a d he' 'fi lh Oils, laid n t o e ame oil, soybeam 'oil, tungbil, corn oil or partially oi" corinpletely hydrogenated uerivauve s of siich'oils, fatty acids derived from 'ca'r'nau a, sperma'ce'tic, beeswax, ca-henna wax and like waxes, andca'rboxylic acids driv'e'dfioiii petroleum'or other hydrocarbons. Other soap-forming acids which may be used are naphthenic acid, tall 'oil fatty acids,tand hydroaromatic acids such as abietic acid and the like.

The following examples are illustrative of the method which may be used to form the complex metal ammine salt of a rosin amine-water insoluble soap reaction product of e p es n ven In he ex ples the term pa s e e to Pa s by we h Example 1 parts of magnesium acetate were added with stirring 3 to 100 parts of 2-ethylhexoic acid at a temperature of 350 to 420 F. The heating and agitation were continued until the acetic acid liberated by the reaction was vaporized. There were then added 100 parts of dehydroabietyl amine and the temperature was permitted to drop to 260 F. At this point 55 parts of copper acetate were added and the temperature was raised to 340 R, where it was maintained for 15 minutes, whereupon a clear solution was obtained and heating discontinued. When the temperature dropped to 175 F., 235 parts of xylol were added. The resulting composition was liquid at room temperature.

The composition of Example 1 was tested to determined I its fungicidal activity by treating duck samples with a xylol solution containing of the reaction product, as follows:

Samples of oz. specification army duck were cut into 10" x 30" pieces and the were washed in soap suds, rinsed and dried. The dried pieces were passed through the testing solution so that complete penetration was obtained. They were then passed through a wringer to remove the excess solution. Approximately a 50% wetpickup was obtained. The treated fabric pieces were then dried for 24 hours to obtain complete solvent release.

The treated and dried pieces of duck were leached for 24 hours in running water and buried horizontally in a well composted soil consisting of 50% back loam and 50% pre-rotted manure, one-half inch below the soil surface. The moisture content of the soil was maintained at approximately 30-50%.

After 28 days incubation in the soil bed, the fabric pieces were removed and examined. There was no evidence of degradation found in the treated fabric pieces after burial and they had retained their original hand characteristics. A control 10" x 30" sample of the aforesaid army duck containing no treatment was buried at the same time as the treated pieces and under the same conditions. The control was completely destroyed, being in the form of small deteriorated pieces at the conclusion of the 28 day test period.

Prior to impregnating the piece of duck with the solution of Example 1, it and the untreated piece of duck was tested for tensile strengths on a 500 lb. vertical Scott tester. Each had a tensile strength of 296 lbs. After the 28 day burial period the treated duck and the control piece were removed from the soil, washed thoroughly in warm water to remove all soil particles and airdried at room temperature. piece was then taken on the same Scott tester. It had a tensile strength of approximately 298 lbs. The control piece was removed from the soil in small deteriorated pieces which had lost their fabric strength and hence were not tested. Each of these small pieces was badly stained. In contrast the treated piece was substantially free from stain.

Example 2 Example 1 was repeated except that 55 parts of zinc acetate were used in lieu of the copper acetate. A test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated pieces showed no sign of degradation and no loss of hand, whereas the control piece had completely deteriorated.

Example 3 Example 1 was repeated except that a corresponding amount of zinc oleate was used in lieu of the magnesium 2-ethylhexoate. A test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated pieces showed no sign of degradation and no loss of hand, whereas the control piece had completely deteriorated.

Tensile strength onv the treated Example 4 Example 5 Example 1 was repeated except that parts of rosin amine made. from wood. rosin were used in lieu of the dehydroabietyl amine. A test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated pieces showed no sign of degradation and no loss of hand, whereas the control piece had completely deteriorated.

Example 6 Example 1 was repeated except that a corresponding amount of nickel Z-ethylhexoate was used in lieu of the magnesium 2-ethylhexoate and a corresponding amount of zinc chloride was used in lieu of the copper acetate. A

test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated'pieces showed no sign of degradation and no loss of hand, whereas the control piece had completely deteriorated;

Example 7 Example 1 was repeated except that 55 parts of silver nitrate were used in lieu of the copper acetate of Example 1. A test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated pieces showed no sign of degradation and no loss of hand," whereas the control piece had completely deteriorated.

Example 8 Example 1 was repeated except that 55 parts of mer curic acetate were used in lieu of the copper acetate of Example 1. A test solution and fabric pieces were made up and tested against an untreated fabric control piece, as described. The treated pieces showed no sign of degradation and no loss of hand, whereas the control piece had completely deteriorated.

The reaction products of each of Examples 1 to ,8, inclusive, in the form of the solutions described, were individually applied to wood samples 1" x 3" and leather squares 2 x 2" by soaking under vacuum for 20 minutes and drying for 6 hours. The treated specimens and untreated control specimens of similar dimensions were placed on a sterile nutrient agar medium with a pH of 5.5, which was used for the substratum in the petri dishes in which the specimens were placed. Each treated specimen and a control specimen were placed in a single petri dish. The specimens in each of these dishes were sprayed with a spore suspension of the following organisms and incubated at 30 C. for 14 days. Chaetomium globosum, Penicillium citrinum, Aspergillus niger, Aspergillus ferreus, T richoderma viride, and Aspergillus flavus.

At the conclusion of this test period it was found that fungi were growing over the entire surface of the leather and wood control specimens and that no growth existed on the treated wood and leather specimens.

The reaction products of the present invention can be used to treat textiles, paper, leather and the like by impregnating or coating these materials with a solution or dispersion of the reaction product in a suitable vehicle. Thus, the solutions described above may be used to treat these materials. These solutions may be compounded with resins, animal, vegetable and fish oils, plasticizers, flameproofing' agents, driers, anti-oxidants and the like, in accordance with known techniques, to impart to the solutions desired properties. For example, characteristics such as spread and flow of these solutions may be modified :the .addition .thereto .ofafatty acid .such as lauricLacid,

oleic acid, linseed oil fatty acids, hempseed oil 'fattyacids and likefatty acids having from .8 to 20 carbon atoms in the chain, and .of a fatty acid .slyceride, either .raw .or treated, .such as raw or bodied linseed oil,.China wood oil, castor' oil, .dehydrated castor oil, and the like. Compatible natural and syntheticresins such as rosin, phenolaldehyde resins, urea-aldehyde resins, vinylresins and .the like, or compatible cellulose derivatives such as, nitrocellulose, cellulose, cellulose acetate, ethly cellulose and the like may be incorporated in the solutions in varying proportions to meetany desiredneeds.

Plasticizers such as glycol, glycerine, pen-taerythritol, :sorbitol, mannitol and other compatible plasticizers may be added to the solutions. Suitable anti-oxidants which may be added to the solution are phenyl sa'licylate, tertiary butyl catechol and guaiacol,.and suitable driers are z'inc naphthenate, lead'naphthenate, cobalt naphtnenate and Zinc octoate.

If it is desired to impart water-proof properties to the solutions of the reaction products of the present invention, various waxes such as parafiin' wax, beeswax, carnauba wax, spermaceti wax, synthetic waxes, and the like, may be incorporatedin the solutions in varying proportions to meet the desired needs.

.By a proper choice of the solvents for the reaction products of the present invention and of suitable moditying agents, the resulting liquid compositions may .be controlled as to consistency, drying time, flow, penetration, and the like.

Other solvents for the reaction products of the present invention are toluol, benzol, carbon tetrachloride, mineral spirits, naphtha, acetone, and the like,

Compositions containing reaction products of the present invention not only inhibit the growth of fungus organisms but may also kill the activity of all existing fungus growth on contact. Textiles, leather, wood, resins, etc., which have been treated with the reaction products of the present invention are not attacked to any appreciable extent by soil animal life and these treated materials resist the action of bacteria and insects. The reaction products of the present invention lend themselves for use as insecticides, in either dry or liquid form, and for preventing and combating diseases of plant life, both those diseases which attack the parts of plants above ground and diseases such as rot which attack underground parts of the plants. In dry form the active ingredient is mixed with an inert diluent such as bentonite, kieselguhr, talc, etc.

While the present invention has been described in connection with certain specific examples of methods of making the reaction products, it is obvious that my invention is not to be construed as limited to the specific materials disclosed in these examples or to the details of the methods set fonth therein, since changes in materials, proportions and method details may be made without departing from the scope of my invention as defined in the appended claims.

I claim:

1. The method of forming a composition of matter comprising heating at an elevated temperature sufiicient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, a metal ammine complex salt of a rosin amine, the metal of said metal ammine complex being from a water-soluble salt of a metal capable of forming a complex with ammonia and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

2. The product produced by the method of claim 1.

3. The method of forming a composition of matter comprising heating at an elevated temperature sufficient to place the reactants into homogeneous solution, said .temperature'being belowthe lowest decomposition temperature of the reactants, a copper amminecomplex salt of a rosin amine and a water-insoluble mono-.carboxylic acid soap having atleast 6 carbon atoms in thecarboxylic acid, said -carboxylic acid being not otherwisesubstituted than with a hydrocarbon radical and the hydroxyl radical.

v 4. The. product produced by the method of claim 3.

5. The method of forming a composition of matter comprising heating at an elevated temperature sutficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, a zinc amminecomplex salt of a. rosin amine and a water-insoluble mono-carboxylic acid soap havingat least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substitutedthan with a hydrocarbon radical and the hydroxyl radical.

6; The product produced by the method of claim 5.

7. The method of forming a composition of matter comprising heating at an elevated temperature sufficient to place the reactants into homogeneous solution, said temperature being below the lowest decompositiontcmperature of thereactants, a silver ammine complex salt of a rosin amine and a water-insoluble mono-carboxylio acid soap-having at least 6 carbon atoms in the carboxylic acid,.said carboxylic acid being not otherwise substituted than with-ahydrocarbonradical and the hydroxyl radical.

8. The ,product produced by the method'of claim 7.

9. The method of forming a composition of matter comprising heating at an elevated temperature suflicient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, a mercury ammine complex salt of a rosin amine and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

10. The product produced by the method of claim 9.

11. The method of forming a composition of matter comprising heating at an elevated temperature sutficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, an aluminum ammine complex salt of a rosin amine and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

12. The product produced by the method of claim 11.

13. The method of forming a composition of matter comprising heating at an elevated temperature sufiicient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, a rosin amine, a water soluble salt of a metal capable of forming a complex with ammonia and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

14. The method of forming a composition of matter comprising heating at an elevated temperature sufiicient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, dehydroabietyl amine, copper acetate and magnesium Z-ethylhexoate.

15. The product produced by the method of claim 14.

16. The method of forming a composition of matter comprising heating at an elevated temperature sufiicient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, dehydroabietyl amine, Zinc acetate and magnesium 2-ethylhexoate.

17. The product produced by the method of claim 16.

18. The method of forming a composition of matter comprising heating at an elevated temperature sutficient to place the reactants into homogeneous solution, said temperature being below the, lowest decomposition temperature of the reactants, dehydroabietyl amine, mercuric acetate and magnesium 2-ethylhexoate.

19. The method of forming a composition of matter comprising heating at an elevated temperature sutficient to place the reactants intohomogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, dehydroabietyl amine, a water soluble copper salt and a water-insoluble mono-carboxylic acid soap having atleast 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical. 20. The method of forming a composition of matter comprising heating at an elevated temperature sutficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, dehydroabietyl amine, a water soluble zinc salt and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical. 21. The method of forming a composition of matter comprising heating at an elevated temperature sufficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperature of the reactants, dehydroabietyl amine, a water soluble silver salt and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

22. The method of forming a composition of matter comprising heating at an elevated temperature sufficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition temperatureof the reactants, dehydroabietyl amine, a water soluble mercury salt and a water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

23. The method of forming a composition of matter comprising heating at an elevated temperature sufficient to place the reactants into homogeneous solution, said temperature being below the lowest decomposition tem perature of the reactants, dehydroabietyl amine, a water soluble aluminum salt and a Water-insoluble mono-carboxylic acid soap having at least 6 carbon atoms in the carboxylic acid, said carboxylic acid being not otherwise substituted than with a hydrocarbon radical and the hydroxyl radical.

References Cited in the file of this patent UNITED STATES PATENTS 2,490,924 Schertz Dec. 13, 1949 2,490,925 Schertz Dec. 13, 1949 2,492,939 Schertz Dec. 27, 1949 2,513,429 Rosher July 4, 1950 2,623,870 Sanders Dec. 30, 1952 

1. THE METHOD OF FORMING A COMPOSITION OF MATTER COMPRISING HEATING AT AN ELEVATED TEMPERATURE SUFFICIENT TO PLACE REACTANTS INTO HOMOGENEOUS SOLUTION, SAID TEMPERATURE BEING BELOW THE LOWEST DECOMPOSITION TEMPERATURE OF THE REACTANTS, A METAL AMMINE COMPLEX SALT OF A ROSIN AMINE, THE METAL OF SAID METAL AMMINE COMPLEX BEING FROM A WATER-INSOLUBLE SALT OF A METAL CAPABLE OF FORMING A COMPLEX WITH AMMONIA AND A WATER-INSOLUBLE MONO-CARBOXYLIC ACID SOAP HAVING AT LEAST 6 CARBON ATOMS IN THE CARBOXYLIC ACID, SAID CARBOXYLIC ACID BEING NOT OTHERWISE SUBSTITUTED THAN WITH A HYDROCARBON RADICAL AND THE HYDROXYL RADICAL. 